PREPARATION AND REACTIONS OF 2-CHLOROETHYL 1-THIO-BETA-D-GLYCOPYRANOSIDES DERIVED FROM D-GALACTOSE, D-GLUCOSE, AND 2-ACETAMIDO-2-DEOXY-D-GLUCOSE

Chloroethyl 1-thio-beta-D-glycopyranosides of the D-galacto and D-gluc o configurations 5a-5c were prepared by alkylation of the correspondin g 1-thio-beta-D-hexopyranoses 3a-3c with 1-bromo-2-chloroethane follow ed by deacetylation. The starting 1-thio-beta-D-hexopyranoses were obt ained from the acetylated glycopyranosyl halides via isothiouronium sa lts. It was demonstrated that the chloroethyl thioglycosides 5a-5c und ergo hydrolysis in aqueous solutions to give the 2-hydroxyethyl thiogl ycosides 6a-6c and reducing hexoses and that this hydrolysis proceeds via episulfonium salts. The hydrolysis was monitored by H-1 and C-13 N MR spectroscopy. In 1% aqueous solutions of sodium carbonate containin g phenol or aniline, the thioglycosides 5a-5c provide, in addition to the above hydrolysis products, also the phenoxyethyl and phenylaminoet hyl thioglycosides 9a, 10a and 9b, 10b, respectively.